Herbicidal antidote compositions with substituted oxazolidines and thiazolidines

ABSTRACT

Herbicidal compositions comprising an active herbicidal compound and antidote therefor and the methods of use; the antidote compound corresponds to substituted oxazolidines and thiazolidines having the formula ##SPC1## 
     In which X is oxygen or sulfur; R is haloalkyl, alkyl or alkylthio; and R 1 , R 2 , R 3 , R 4 , R 5  and R 6  are independently selected from the group consisting of hydrogen, lower alkyl, alkoxyalkyl and lower alkylol.

CROSS REFERENCE TO RELATED APPLICATION

This application is a continuation-in-part of copending application Ser. No. 297,561, filed Oct. 13, 1972 now abandoned, which in turn is a continuation-in-part of copending application Ser. No. 208,041, filed Dec. 9, 1971, which in turn is a continuation-in-part of then copending application, Ser. No. 134,868, filed Apr. 16, 1971, now abandoned.

BACKGROUND OF THE INVENTION

Among the many herbicidal compounds commercially available, the thiocarbamates alone or admixed with other herbicides, such as the triazines, have reached a relatively high degree of commercial success. These herbicides are immediately toxic to a large number of weed pests at different concentrations varying with the resistance of the weed pests. Some examples of these compounds are described and claimed in U.S. Pat. Nos. 2,913,327, 3,037,853, 3,175,897, 3,185,720, 3,198,786 and 3,582,314. It has been found in practice that the use of these thiocarbamates as herbicides on crops sometimes causes serious injuries to the crop plant. When used in the recommended amounts in the soil to control many broadleaf weeds and grasses, serious malformation and stunting of the crop plants result. This abnormal growth in the crop plants results in loss of crop yield. Previous attempts to overcome this problem involves the treatment of the crop seed with certain antagonistic agents prior to planting, see U.S. Pat. Nos. 3,131,509 and 3,564,768. These antagonistic agents have not been notably successful. The aforementioned patent specifically exemplifies the treatment of seeds employing compounds of a different chemical class not suggestive of the present invention.

Other preferred herbicidal compounds whose effect can be modified by the instant compounds include the acetanilides, such as 2-chloro-2',6'-diethyl-N-(methoxymethyl)acetanilide and the urea-type herbicides, such as 3-(3,4-dichlorophenyl)-1,1-dimethylurea.

DESCRIPTION OF THE INVENTION

It has been discovered that plants can be protected against injury by the thiolcarbamate-type herbicides, alone or mixed with other compounds and/or the tolerance of the plants can be substantially increased to the active compounds of the above-noted U.S. Patents by adding to the soil an antidote compound corresponding to the following formula: ##SPC2##

In which X is oxygen or sulfur; R is haloalkyl, alkyl or alkylthio; and R₁, R₂, R₃, R₄, R₅ and R₆ are independently selected from the group consisting of hydrogen, lower alkyl, alkoxyalkyl and lower alkylol.

In the above description, the following embodiments are intended for the various substituent groups: for R, haloalkyl and alkyl preferably includes, unless otherwise provided for, those members which contain from 1 to 10 carbon atoms, inclusive, in both straight chain and branched chain configurations, and the term halo includes chloro and bromo as mono, di, tri, tetra and per substitutions. As exemplary of the alkyl portion within the preferred embodiment are the following: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, 1,1-dimethylbutyl, amyl, isoamyl, 2,4,4-trimethylpentyl, n-hexyl, isohexyl, n-heptyl, n-octyl, isooctyl, nonyl, and decyl. The term alkylthio preferably includes those members which contain from 1 to 4 carbon atoms, inclusive, for example, methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, t-butylthio, and the like. For R₁, R₂, R₃, R₄, R₅ and R₆, the term lower alkyl preferably includes, unless otherwise provided for, those members which contain from 1 to 4 carbon atoms, inclusive, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, tert.-butyl, and the like. The term alkoxyalkyl preferably includes those members having a total of 2 to 4 carbon atoms, inclusive, for example, methoxymethyl, methoxyethyl, ethoxyethyl, ethoxymethyl and the like. The term lower alkylol preferably includes those members having 1 to 4 carbon atoms, inclusive, for example, methylol, ethylol, propylol and butylol.

As an alternative mode of action, the compounds of this invention may interfere with the normal herbicidal action of the thiocarbamate-type and other herbicides to render them selective in their action. Whichever mode of action is present, the corresponding beneficial and desirable effect is the continued herbicidal effect of the thiocarbamate with the accompanying decreased herbicidal effect on desired crop species. This advantage and utility will become more apparent hereinafter.

Therefore, the terms herbicide, antidote or antidotal amount, is meant to describe that effect which tends to counteract the normal injurious herbicidal response that the herbicide might otherwise produce. Whether it is to be termed a remedy, interferant, protectant, or the like, will depend upon the exact mode of action. The mode of action is varied, but the effect, which is desirable, is the result of the method of treating the soil in which a crop is planted. Hitherto, there have been no systems which have been satisfactory for this purpose.

The compounds of this invention represented by the above formula can be prepared by several different procedures depending upon the starting materials.

The oxazolidine and thiazolidine intermediates were prepared by the condensation of the amino alcohol or mercaptan with a suitable aldehyde or ketone in boiling benzene with the continuous separation of water. This method is described by Bergmann et al., JACS 75 358 (1953). Usually, the oxazolidines and thiazolidines intermediates were pure enough to be used directly without further purification. Aliquots of these solutions were then used to prepare the compounds of this invention.

The appropriate intermediate was reacted with an acid chloride in the presence of a hydrogen chloride acceptor, such as triethylamine, to prepare the desired compound. Workup and purification procedures involved standard methods of extration, distillation or crystallization.

The compounds of the present invention and their preparation are more particularly illustrated by the following examples. Following the examples of preparation is a table of compounds which are prepared according to the procedures described herein. Compound numbers have been assigned to them and are used for identification throughout the balance of the specification.

EXAMPLE IA Preparation of 2,2-dimethyl-3-dichloroacetyl oxazolidine

Five and one-tenth (5.1 g.) grams of 2,2-dimethyl oxazolidine dissolved in 50 ml. of benzene was treated with 5.5 g. of triethylamine and 7.4 g. of dichloroacetyl chloride was added dropwise with stirring and cooling in an ice bath. The mixture was poured into water, the benzene solution separated, dried over anhydrous magnesium sulfate and the solvent stripped under vacuum. The product was a waxy solid which had a melting point of 113°-115° C. on recrystallization from diethyl ether.

EXAMPLE IB ##SPC3##

15 g. of acetone and 12.2 g. of ethanol amine were combined in 150 ml. of benzene and refluxed until no additional water came over. The resulting solution was examined and found to contain 2,2-dimethyl-1,3-oxazolidine. A quarter of the benzene solution (0.05 mole) was reacted with 7.4 g. of dichloroacetyl chloride and 5.5 g. of triethylamine, washed with water, dried and stripped under vacuum to give a light tan solid. A portion was recrystallized from ether giving a white product.

EXAMPLE II Preparation of 2,2,5-trimethyl-3-dichloroacetyl oxazolidine

Eighteen (18) milliliters of a benzene solution containing 4.6 g. of 2,2,5-trimethyl oxazolidine was added to 25 ml. of benzene and 4.5 g. of triethylamine. Five and nine-tenths (5.9 g.) grams of dichloroacetyl chloride was added dropwise with stirring and cooling in an ice bath. When reaction was complete the mixture was poured into water and the benzene layer separated, dried over anhydrous magnesium sulfate and the benzene removed under vacuum. Yield was 7.7 g. of an oil, n_(D) ³⁰ = 1.4950.

EXAMPLE III Preparation of 2,2-dimethyl-3-dichloroacetyl thiazolidine

Four and seven-tenths (4.7 g.) grams of 2,2-dimethyl thiazolidine and 4.5 g. of triethylamine were dissolved in 50 ml. of methylene chloride and 5.9 g. of dichloroacetyl chloride was added dropwise with stirring. The mixture was cooled in a water bath at room temperature.

When reaction was complete, the mixture was poured into water and the solvent layer separated, dried over anhydrous magnesium sulfate, and the solvent removed under vacuum. Yield was 3.6 g. of a waxy solid. Recrystallization of another sample from diethyl ether gave a white solid, m.p. 109°-111° C.

EXAMPLE IV Preparation of 2,2,5-trimethyl-3(2',3'-dibromopropionyl)oxazolidine

Fourteen (14 ml.) milliliters of a benzene solution containing 3.5 g. of 2,2,5-trimethyl oxazolidine was added to 25 ml. of benzene and 3.5 g. of triethylamine. Seven and one-half (7.5 g.) grams of 2,3-dibromopropionyl chloride was added dropwise with stirring and cooling in an ice bath. When reaction was complete, the mixture was poured into water and the benzene layer separated, dried over anhydrous magnesium sulfate and the solvent stripped under vacuum. The yield was 5.7 g. of an oil, n_(D) ³⁰ = 1.5060.

EXAMPLE V Preparation of 2,2-dimethyl-3-dibromoacetyl thiazolidine

To a mixture of 3.5 g. of 2,2-dimethyl thiazolidine, 50 ml. of benzene and 7.1 g. of dibromoacetyl chloride mixed in an ice bath was added 3.1 g. of triethylamine dropwise with stirring and continued cooling. When reaction was complete, the mixture was poured into water and the benzene layer separated, dried over magnesium sulfate and the benzene removed under vacuum. Yield was 8.5 g. of a dark oil.

EXAMPLE VI Preparation of 2-ethyl-3-S-ethylthiocarbonyl oxazolidine

Sixteen and one half (16.5 ml.) milliliters of a benzene solution of 2-ethyl oxazolidine was added to 50 ml. of benzene and 4.1 g. of triethylamine. Five (5 g.) grams of ethyl chlorothiolformate was added dropwise with stirring and cooling in an ice bath. The mixture was poured into water and the benzene solution separated, dried over anhydrous magnesium sulfate and the benzene stripped under vacuum. Yield was 5.6 g. of an oil, n_(D) ³⁰ = 1.5130.

EXAMPLE VII Preparation of 2,2-dimethyl-3-heptanoyl oxazolidine

Sixteen and one-half (16.5 ml.) milliliters of a benzene solution containing 4.6 g. of 2,2-dimethyl oxazolidine was added to 50 ml. of benzene and 4.1 g. of triethylamine. to this mixture 6 g. of n-heptanoyl chloride was added dropwise with stirring and cooling in an ice bath. The mixture was poured into water and the benzene layer extracted, dried over magnesium sulfate and the benzene removed under vacuum. Yield was 7.5 g. of an oil, n_(D) ³⁰ = 1.4598.

                                      TABLE I                                      __________________________________________________________________________      ##STR1##                                                                      COMPOUND                                     m.p. ° C.                  NUMBER R        R.sub.1                                                                              R.sub.2                                                                             R.sub.3                                                                            R.sub.4                                                                             R.sub.5                                                                            R.sub.6                                                                           X or n.sub.D.sup.                   __________________________________________________________________________                                                  30                                1      CHCl.sub.2                                                                              CH.sub.3                                                                             CH.sub.3                                                                            H   H    H   H  O 116-118                           2      CH.sub.2 Cl                                                                             CH.sub.3                                                                             CH.sub.3                                                                            H   H    H   H  O 1.4932                            3      CBr.sub.3                                                                               CH.sub.3                                                                             CH.sub.3                                                                            H   H    H   H  O 1.5560                            4      CBr.sub.3                                                                               CH.sub.3                                                                             CH.sub.3                                                                            H   H    CH.sub.3                                                                           H  O Glass                             5      CH.sub.2 Cl                                                                             CH.sub.3                                                                             CH.sub.3                                                                            H   H    CH.sub.3                                                                           H  O 1.4842                            6      CHCl.sub.2                                                                              CH.sub.3                                                                             CH.sub.3                                                                            H   H    CH.sub.3                                                                           H  O 1.4950                            7      CH.sub.2 Cl                                                                             CH.sub.3                                                                             CH.sub.3                                                                            C.sub.2 H.sub.5                                                                    H    H   H  O 1.4900                            8      CHCl.sub.2                                                                              CH.sub.3                                                                             CH.sub.3                                                                            C.sub.2 H.sub.5                                                                    H    H   H  O 1.4950                            9      CCl.sub.3                                                                               CH.sub.3                                                                             CH.sub.3                                                                            C.sub.2 H.sub.5                                                                    H    H   H  O 1.4970                            10     CBr.sub.3                                                                               CH.sub.3                                                                             CH.sub.3                                                                            C.sub.2 H.sub.5                                                                    H    H   H  O 1.5428                            11     CH.sub.3 CHBr                                                                           CH.sub.3                                                                             CH.sub.3                                                                            H   H    CH.sub.3                                                                           H  O 1.4993                            12     CH.sub.3 CHBr                                                                           CH.sub.3                                                                             CH.sub.3                                                                            C.sub.2 H.sub.5                                                                    H    H   H  O 1.4993                            13     CH.sub.2 Cl                                                                             CH.sub.3                                                                             C.sub.2 H.sub.5                                                                     H   H    H   H  O 1.4928                            14     CHCl.sub.2                                                                              CH.sub.3                                                                             C.sub.2 H.sub.5                                                                     H   H    H   H  O 1.4982                            15     CCl.sub.3                                                                               CH.sub.3                                                                             C.sub.2 H.sub.5                                                                     H   H    H   H  O 1.5034                            16     CH.sub.3 CHBr                                                                           CH.sub.3                                                                             C.sub.2 H.sub.5                                                                     H   H    H   H  O 1.5058                            17     CBr.sub.3                                                                               CH.sub.3                                                                             C.sub.2 H.sub.5                                                                     H   H    H   H  O 95-97                             18     CH.sub.2 Br                                                                             CH.sub.3                                                                             C.sub.2 H.sub.5                                                                     H   H    H   H  O 1.5097                            19     CH.sub.2 Br                                                                             CH.sub.3                                                                             CH.sub.3                                                                            H   H    CH.sub. 3                                                                          H  O 1.5020                            20     CH.sub.2 Br                                                                             CH.sub.3                                                                             CH.sub.3                                                                            C.sub.2 H.sub.5                                                                    H    H   H  O 1.5048                            21     CH.sub.3 (CHBr).sub.4                                                                   CH.sub.3                                                                             CH.sub.3                                                                            H   H    H   H  O 1.5658                            22     CH.sub.2 Cl                                                                             CH.sub.3                                                                             CH.sub.3                                                                            CH.sub.3                                                                           CH.sub.3                                                                            H   H  O 1.4843                            23     CHCl.sub.2                                                                              CH.sub.3                                                                             CH.sub.3                                                                            CH.sub.3                                                                           CH.sub.3                                                                            H   H  O 120-123                           24     CCl.sub.3                                                                               CH.sub.3                                                                             CH.sub.3                                                                            CH.sub.3                                                                           CH.sub.3                                                                            H   H  O 1.5031                            25     CH.sub.2 Br                                                                             CH.sub.3                                                                             CH.sub.3                                                                            CH.sub.3                                                                           CH.sub.3                                                                            H   H  O 1.5116                            26     CH.sub.3 CHBr                                                                           CH.sub.3                                                                             CH.sub.3                                                                            CH.sub.3                                                                           CH.sub.3                                                                            H   H  O 1.5140                            27     CBr.sub.3                                                                               CH.sub.3                                                                             CH.sub.3                                                                            CH.sub.3                                                                           CH.sub.3                                                                            H   H  O 1.5610                            28     ClCH.sub.2 CH.sub.2                                                                     CH.sub.3                                                                             CH.sub.3                                                                            H   H    H   H  O 1.4538                            29     CHCl.sub.2                                                                              C.sub.2 H.sub.5                                                                      H    H   H    H   H  S 1.5458                            30     CHCl.sub.2                                                                              CH.sub.3                                                                             CH.sub.3                                                                            H   H    H   H  S 109-111                           31     CH.sub.2 BrCHBr                                                                         CH.sub.3                                                                             C.sub.2 H.sub.5                                                                     H   H    H   H  O 1.5170                            32     CH.sub.2 BrCHBr                                                                         CH.sub.3                                                                             CH.sub.3                                                                            H   H    CH.sub.3                                                                           H  O 1.5060                            33     CH.sub.2 BrCHBr                                                                         CH.sub.3                                                                             CH.sub.3                                                                            C.sub.2 H.sub.5                                                                    H    H   H  O 1.5083                            34     CH.sub.2 BrCHBr                                                                         CH.sub.3                                                                             CH.sub.3                                                                            H   H    H   H  O 1.5178                            35     CH.sub.2 BrCHBr                                                                         CH.sub.3                                                                             t-C.sub.4 H.sub.9                                                                   H   H    H   H  O 1.5165                            36     CHCl.sub.2                                                                              CH.sub.3                                                                             t-C.sub.4 H.sub.9                                                                   H   H    H   H  O 1.4949                            37     CBr.sub.3                                                                               CH.sub.3                                                                             t-C.sub.4 H.sub.9                                                                   H   H    H   H  O 1.5431                            38     CHCl.sub.2                                                                              H     H    CH.sub.3                                                                           CH.sub.3                                                                            H   H  O 1.5033                            39     CHCl.sub.2                                                                              CH.sub.3 OCH.sub.2                                                                   H    H   H    H   H  O 1.5132                            40     CHCl.sub.2                                                                              C.sub.3 H.sub.7                                                                      H    H   H    H   H  O 1.4988                            41     CHCl.sub.2                                                                              C.sub.2 H.sub.5                                                                      H    H   H    H   H  O 1.5126                            42     CHBr.sub.2                                                                              C.sub.2 H.sub.5                                                                      H    H   H    H   H  O 1.5750                            43     CBr.sub.3                                                                               C.sub.2 H.sub.5                                                                      H    H   H    H   H  O 1.5610                            44     CH.sub.2 Br                                                                             C.sub.2 H.sub.5                                                                      H    H   H    H   H  O 1.5200                            45     CH.sub.3 CHBr                                                                           C.sub.2 H.sub.5                                                                      H    H   H    H   H  O 1.5140                            46     (CH.sub.3).sub.2 CBr                                                                    C.sub. 2 H.sub.5                                                                     H    H   H    H   H  O 1.4958                            47     CH.sub.2 BrCHBr                                                                         C.sub.2 H.sub.5                                                                      H    H   H    H   H  O 1.5273                            48     CH.sub.2 Cl                                                                             C.sub.2 H.sub.5                                                                      H    H   H    H   H  O 1.5020                            49     CHCl.sub.2                                                                              C.sub.2 H.sub.5                                                                      H    H   H    CH.sub.3                                                                           H  O 1.4955                            50     CH.sub.2 Cl                                                                             C.sub.2 H.sub.5                                                                      H    H   H    CH.sub.3                                                                           H  O 1.4890                            51     CH.sub.2 Br                                                                             C.sub.2 H.sub.5                                                                      H    H   H    CH.sub.3                                                                           H  O 1.5064                            52     CHBr.sub.2                                                                              C.sub.2 H.sub.5                                                                      H    H   H    CH.sub.3                                                                           H  O Glass                             53     CBr.sub.3                                                                               C.sub.2 H.sub.5                                                                      H    H   H    CH.sub.3                                                                           H  O Glass                             54     CH.sub.3 CHBr                                                                           C.sub.2 H.sub.5                                                                      H    H   H    CH.sub.3                                                                           H  O 1.4978                            55     CH.sub.2 BrCHBr                                                                         C.sub.2 H.sub.5                                                                      H    H   H    CH.sub.3                                                                           H  O 1.5138                            56     (CH.sub.3).sub.2 CBr                                                                    C.sub.2 H.sub.5                                                                      H    H   H    CH.sub.3                                                                           H  O 1.4851                            57     CHCl.sub.2                                                                              H     H    C.sub.2 H.sub.5                                                                    H    H   H  O 1.5030                            58     CHBr.sub.2                                                                              H     H    C.sub.2 H.sub.5                                                                    H    H   H  O Dark liquid                       59     CBr.sub.3                                                                               H     H    C.sub.2 H.sub.5                                                                    H    H   H  O 1.5531                            60     CH.sub.2 Br                                                                             H     H    C.sub.2 H.sub.5                                                                    H    H   H  O 1.5173                            61     CH.sub.3 CHBr                                                                           H     H    C.sub.2 H.sub.5                                                                    H    H   H  O 1.5076                            62     (CH.sub.3).sub.2 CBr                                                                    H     H    C.sub.2 H.sub.5                                                                    H    H   H  O 1.4852                            63     CH.sub.2 BrCHBr                                                                         H     H    C.sub.2 H.sub.5                                                                    H    H   H  O 1.5249                            64     CCl.sub.3                                                                               H     H    C.sub.2 H.sub.5                                                                    H    H   H  O 1.5048                            65     CH.sub.2 Cl                                                                             H     H    C.sub.2 H.sub.5                                                                    H    H   H  O 1.4998                            66     CHCl.sub.2                                                                              CH.sub.3                                                                             H    H   H    H   H  O 1.5112                            67     CCl.sub.3                                                                               CH.sub.3                                                                             H    H   H    H   H  O 1.5148                            68     CH.sub.2 Cl                                                                             CH.sub.3                                                                             H    H   H    H   H  O 1.5077                            69     CH.sub.2 Br                                                                             CH.sub.3                                                                             H    H   H    H   H  O 1.5263                            70     CHBr.sub.2                                                                              CH.sub.3                                                                             H    H   H    H   H  O 1.5471                            71     CBr.sub.3                                                                               CH.sub.3                                                                             H    H   H    H   H  O Dark liquid                       72     CH.sub.2 BrCHBr                                                                         CH.sub.3                                                                             H    H   H    H   H  O 1.5280                            73     CH.sub.3 CHBr                                                                           CH.sub.3                                                                             H    H   H    H   H  O 1.5162                            74     (CH.sub.3).sub.2 CBr                                                                    CH.sub.3                                                                             H    H   H    H   H  O 1.5013                            75     CHCl.sub.2                                                                              CH.sub.3                                                                             H    H   H    CH.sub.3                                                                           H  O 1.4983                            76     CCl.sub.3                                                                               CH.sub.3                                                                             H    H   H    CH.sub.3                                                                           H  O 1.4990                            77     CH.sub.2 Cl                                                                             CH.sub.3                                                                             H    H   H    CH.sub.3                                                                           H  O 1.4958                            78     CHBr.sub.2                                                                              CH.sub.3                                                                             H    H   H    CH.sub.3                                                                           H  O Dark liquid                       79     CH.sub.3 CHBr                                                                           CH.sub.3                                                                             H    H   H    CH.sub.3                                                                           H  O 1.5083                            80     CHBr.sub.2                                                                              C.sub.2 H.sub.5                                                                      H    H   H    H   H  S 1.5782                            81     CH.sub.2 BrCHBr                                                                         C.sub.2 H.sub.5                                                                      H    H   H    H   H  S 1.5650                            82     CCl.sub.3                                                                               CH.sub.3                                                                             CH.sub.3                                                                            H   H    H   H  S 1.5638                            83     CHBr.sub.2                                                                              CH.sub.3                                                                             CH.sub.3                                                                            H   H    H   H  S Dark liquid                       84     CH.sub.3 CHBr                                                                           CH.sub.3                                                                             CH.sub.3                                                                            H   H    H   H  S 1.5520                            85     CHCl.sub.2                                                                              H     H    H   H    H   H  S 75-77                             86     CHCl.sub.2                                                                              CH.sub.3                                                                             i-C.sub.3 H.sub.7                                                                   H   H    H   H  O 1.4960                            87     CHCl.sub.2                                                                              CH.sub.3                                                                             CH.sub.3                                                                            CH.sub.3                                                                           CH.sub.2 OH                                                                         H   H  O 1.4960                            88     CH.sub.2 BrC(CH.sub.3)Br                                                                C.sub.2 H.sub.5                                                                      H    H   H    H   H  O 1.5318                            89     CH.sub.2 BrC(CH.sub.3)Br                                                                C.sub.2 H.sub.5                                                                      H    H   H    CH.sub.3                                                                           H  O 1.5225                            90     CH.sub.2 BrC(CH.sub.3)Br                                                                CH.sub.3                                                                             H    H   H    CH.sub.3                                                                           H  O 1.5210                            91     CHCl.sub.2                                                                              C.sub.2 H.sub.5                                                                      H    C.sub.2 H.sub.5                                                                    H    H   H  O 1.4947                            92     C.sub.2 H.sub.5 S                                                                       H     H    C.sub.2 H.sub.5                                                                    H    H   H  O 1.4998                            93     C.sub.2 H.sub.5 S                                                                       CH.sub.3                                                                             H    H   H    CH.sub.3                                                                           H  O 1.4965                            94     C.sub.2 H.sub.5 S                                                                       C.sub.2 H.sub.5                                                                      H    H   H    CH.sub.3                                                                           H  O 1.4973                            95     C.sub.2 H.sub.5 S                                                                       C.sub.2 H.sub.5                                                                      H    C.sub.2 H.sub.5                                                                    H    H   H  O 1.4928                            96     CCl.sub.3                                                                               C.sub.2 H.sub.5                                                                      H    C.sub.2 H.sub.5                                                                    H    H   H  O 1.4937                            97     CH.sub.2 BrCHBr                                                                         C.sub.2 H.sub.5                                                                      H    C.sub.2 H.sub.5                                                                    H    H   H  O 1.5198                            98     CH.sub.2 BrC(CH.sub.3)Br                                                                C.sub.2 H.sub.5                                                                      H    C.sub.2 H.sub.5                                                                    H    H   H  O 1.5202                            99     CH.sub.2 BrCH.sub.2                                                                     C.sub.2 H.sub.5                                                                      H    C.sub.2 H.sub.5                                                                    H    H   H  O 1.4920                             100   CHCl.sub.2                                                                              CH.sub.3                                                                             H    C.sub.2 H.sub.5                                                                    H    H   H  O 1.4960                             101   C.sub.3 H.sub.7 S                                                                       CH.sub.3                                                                             H    C.sub.2 H.sub.5                                                                    H    H   H  O 1.4900                             102   i-C.sub.3 H.sub.7 S                                                                     CH.sub.3                                                                             H    C.sub.2 H.sub.5                                                                    H    H   H  O 1.4875                             103   CCl.sub.3                                                                               CH.sub.3                                                                             H    C.sub.2 H.sub.5                                                                    H    H   H  O 1.4990                             104   CH.sub.2 Br                                                                             CH.sub.3                                                                             H    C.sub.2 H.sub.5                                                                    H    H   H  O 1.5070                             105   CH.sub.2 BrCHBr                                                                         CH.sub.3                                                                             H    C.sub.2 H.sub.5                                                                    H    H   H  O 1.5168                             106   CH.sub.2 BrC(CH.sub.3)Br                                                                CH.sub.3                                                                             H    C.sub.2 H.sub.5                                                                    H    H   H  O 1.5160                             107   CH.sub.2 BrCH.sub.2                                                                     CH.sub.3                                                                             H    C.sub.2 H.sub.5                                                                    H    H   H  O 1.4950                             108   C.sub.4 H.sub.9 S                                                                       CH.sub.3                                                                             H    C.sub.2 H.sub.5                                                                    H    H   H  O 1.4928                             109   C.sub.4 H.sub.9 S                                                                       C.sub.2 H.sub.5                                                                      H    C.sub.2 H.sub.5                                                                    H    H   H  O 1.4880                             110   CH.sub.3 S                                                                              CH.sub.3                                                                             H    C.sub.2 H.sub.5                                                                    H    H   H  O 1.4980                             111   C.sub.6 H.sub.13                                                                        CH.sub.3                                                                             CH.sub.3                                                                            H   H    H   H  O 1.4598                             112   CH.sub.3 S                                                                              CH.sub.3                                                                             CH.sub.3                                                                            C.sub.2 H.sub.5                                                                    H    H   H  O 1.4913                             113   n-C.sub.3 H.sub.7 S                                                                     CH.sub.3                                                                             CH.sub.3                                                                            C.sub.2 H.sub.5                                                                    H    H   H  O 1.4858                             114   i-C.sub.3 H.sub.7 S                                                                     CH.sub.3                                                                             CH.sub.3                                                                            C.sub.2 H.sub.5                                                                    H    H   H  O 1.4828                             115   CH.sub.2 BrCH.sub.2                                                                     CH.sub.3                                                                             CH.sub.3                                                                            H   H    H   H  O 1.4912                             116   CH.sub.2 BrCHBr                                                                         H     H    CH.sub.3                                                                           CH.sub.3                                                                            H   H  O 1.5221                             117   CH.sub.2 BrCH.sub.2                                                                     CH.sub.3                                                                             CH.sub.3                                                                            H   H    H   H  S 1.5263                             118   CH.sub.2 BrCHBr                                                                         CH.sub.3                                                                             CH.sub.3                                                                            H   H    H   H  S 1.5573                             119   CH.sub.2 BrCH.sub.2                                                                     H     H    CH.sub.3                                                                           CH.sub.3                                                                            H   H  O 1.4890                             120   CH.sub.2 Br                                                                             H     H    H   H    H   H  S 1.6032                             121   CH.sub.3 CHBr                                                                           H     H    H   H    H   H  S 1.5720                             122   CH.sub.2 BrCH.sub.2                                                                     H     H    H   H    H   H  S 1.5629                             123   CH.sub. 2 BrCHBr                                                                        H     H    H   H    H   H  S 1.5742                             124   CH.sub.3 C(CH.sub.3)Br                                                                  H     H    H   H    H   H  S 1.5420                             125   CH.sub.2 ClCH.sub.2                                                                     H     H    H   H    H   H  S 1.5475                             126   BrCH.sub.2 (CH.sub.2).sub.8 CH.sub.2                                                    CH.sub.3                                                                             CH.sub.3                                                                            H   H    H   H  O 1.4898                             127   ClCH.sub.2 CH.sub.2 CH.sub.2                                                            CH.sub.3                                                                             CH.sub.3                                                                            H   H    H   H  O 1.4880                             128   ClCH.sub.2 CH.sub.2 CH.sub.2                                                            CH.sub.3                                                                             CH.sub.3                                                                            H   H    H   H  S 1.5183                             129   CH.sub.3 CHClCH.sub.2                                                                   CH.sub.3                                                                             CH.sub.3                                                                            H   H    H   H  O 1.4896                             130   CH.sub.3 CHClCH.sub.2                                                                   CH.sub.3                                                                             CH.sub.3                                                                            H   H    H   H  S 1.5115                             131   CH.sub.3 CHClCH.sub.2                                                                   CH.sub.3                                                                             CH.sub.3                                                                            H   H    CH.sub.3                                                                           H  O 1.4701                             132   C.sub.2 H.sub.5 CHBr                                                                    CH.sub.3                                                                             CH.sub.3                                                                            H   H    H   H  O 1.5020                             133   C.sub.2 H.sub.5 CHBr                                                                    CH.sub.3                                                                             CH.sub.3                                                                            H   H    H   H  S 1.5288                             134   C.sub.2 H.sub.5 CHBr                                                                    CH.sub.3                                                                             CH.sub.3                                                                            H   H    CH.sub.3                                                                           H  O 1.4900                             135   C.sub.3 H.sub.7 CHBr                                                                    CH.sub.3                                                                             CH.sub.3                                                                            H   H    H   H  O 1.4972                             136   C.sub.3 H.sub.7 CHBr                                                                    CH.sub.3                                                                             CH.sub.3                                                                            H   H    H   H  S 1.5220                             137   C.sub.3 H.sub.7 CHBr                                                                    CH.sub.3                                                                             CH.sub.3                                                                            H   H    CH.sub.3                                                                           H  O 1.4870                             138   CH.sub.2 ClCH.sub.2 CH.sub.2                                                            CH.sub.3                                                                             CH.sub.3                                                                            H   H    CH.sub.3                                                                           H  O 1.4747                             139   CH.sub.2 Br(CH.sub.2).sub.4                                                             CH.sub.3                                                                             CH.sub.3                                                                            H   H    H   H  O 1.4970                             140   CH.sub.2 Br(CH.sub.2).sub.4                                                             CH.sub.3                                                                             CH.sub.3                                                                            H   H    CH.sub.3                                                                           H  O 1.4886                             141   CH.sub.2 Br(CH.sub.2).sub.4                                                             CH.sub.3                                                                             CH.sub.3                                                                            H   H    H   H  S 1.5249                             142   CHCl.sub.2                                                                              H     H    H   H    H   H  O 1.5136                             143   CH.sub.2 BrCBr(CH.sub.3)                                                                H     H    H   H    H   H  S Semi-solid                         144   CH.sub.2 Cl                                                                             H     H    H   H    H   H  S 1.5540                             145   CHCl.sub.2                                                                              CH.sub.3                                                                             C.sub.2 H.sub.5                                                                     H   H    H   H  S 1.5443                             146   CH.sub.3 CHBr                                                                           CH.sub.3                                                                             C.sub.2 H.sub.5                                                                     H   H    H   H  S 1.4327                             147   CH.sub.2 BrCH.sub.2                                                                     CH.sub.3                                                                             C.sub.2 H.sub.5                                                                     H   H    H   H  S 1.4293                             148   CH.sub.2 Cl                                                                             CH.sub.3                                                                             C.sub.2 H.sub.5                                                                     H   H    H   H  S 1.5279                            __________________________________________________________________________

The compounds of this invention were employed in effective herbicidal antidote compositions comprising thiocarbamates in combination with antidote compounds described hereinabove. They were tested in the following manner.

Corn Seed Treatment Test

Small flats were filled with Felton loamy sand soil. Soil incorporated herbicides were applied at this time. The soil from each flat was placed into a five-gallon cement mixer where the soil was mixed as the herbicides were applied using a predetermined amount of a stock solution containing 936 mg. of 75.5% active ingredient to 100 ml. of water. One ml. of stock solution was applied to the soil in a volumetric pipet for each pound of herbicide desired. One ml. of stock solution contained 7 mg. of herbicide which equals one pound per acre when applied to the soil in the flats. After the herbicide incorporation, the soil was placed back into the flats.

Flats of herbicide-treated and untreated soil were then ready to be planted. A pint sample of soil was removed from each flat and placed next to each flat for later use in covering up the seeds. The soil was leveled and rows one-half inch deep were made for planting seeds. Alternating rows of treated and untreated crop seeds were sown. In each test, six PAG 344T field corn seeds were planted in each row. Rows were approximately 11/2 inches apart in the flat. Seed were treated by either (1) placing 50 mg. of the antidote compound with 10 grams of corn seed (0.5% w/w) in a suitable container and shaking them until the seeds were uniformly covered with the compound, or (2) preparing a stock solution by dissolving 50 mg. of the antidote compound in 5 ml. of acetone, then using 0.5 ml. of the stock solution to treat 10 g. of corn seed (0.05% w/w). Antidote compounds were also applied as liquid slurries and powders or dusts. In some cases, acetone was used to dissolve powdered or solid compounds so they could be more effectively applied to the seeds.

After the flats were seeded, they were covered with the one pint of soil which had been removed just prior to planting. Flats were placed on greenhouse benches where temperatures ranged from 70°-90° F. Flats were watered by sprinkling as needed to assure good plant growth. Per cent control ratings were taken two, three and four weeks after the treatments were applied.

In each test, the herbicide was applied alone, in combination with the seed protectant, and the seed protectant was applied alone to check for phytotoxicity. The untreated adjacent row was employed to observe any beneficial lateral movement of the antidote compound through the soil. The degree of the effect was noted by comparison with the control. The results of these tests are tabulated in Table II.

                  TABLE II                                                         ______________________________________                                         Per Cent Injury to Corn from EPTC*                                             Seed Treatment Test                                                                      Per Cent Injury, 2 weeks                                                             Treated       Untreated                                        COMPOUND        Seed          Seed                                             NUMBER          (0.05% w/w)   Adjacent Row                                     ______________________________________                                         1                0          0                                                  1     **        5          30                                                  2               70         80                                                  3     **        40         60                                                  4               10         50                                                  5               30         60                                                  6               0          0                                                   7               40         55                                                  8               0          15                                                  9               10         55                                                  10              20         60                                                  11              30         50                                                  12              10         40                                                  13              50         70                                                  14              0          20                                                  15              20         50                                                  16              10         55                                                  17              30         50                                                  18              20         50                                                  19              40         50                                                  20              20         60                                                  21              50         50                                                  22              60         60                                                  23              50         60                                                  24              20         60                                                  25              20         70                                                  26              20         60                                                  27              20         60                                                  28              60         70                                                  29              0          5                                                   30              20         5                                                   142   ***       10         75                                                  EPTC 6E     --                  70                                             Untreated Seed                  80 (4 weeks)                                   ______________________________________                                           * = S-ethyl dipropylthiocarbamate 6E: 6 lb/A preplant incorporated             ** = Seed treatment 0.01% w/w                                                 *** = Seed treatment 0.5% w/w                                            

With 2-chloro-2',6'-diethyl-N-(methoxymethyl)acetanilide at 2 lb/A as a seed treatment, 0.5%, Compound No. 145 gave 100% protection to sorghum (Milo).

Procedure: Multicrop Antidote Screen

Plastic flats were filled with Felton loamy sand soil. Since a variety of grass and broadleaf crops were used in these tests, EPTAM (EPTC) was incorporated at 1/2 and 5 lb/A, while a constant rate of 5 lb/A of the additive was used. EPTAM (EPTC) and the herbicide additive were applied separately by pipetting measured amounts of the appropriate stock solutions into the soil during incorporation in a 5 gallon rotary cement mixer. Stock solutions for EPTAM were prepared as follows:

A. 1/2 lb/A: 670 mg. of EPTC 6E (75.5% a.i.) was diluted with 500 ml. of deionized water so that 2 ml. equals 1/2 lb/A/plastic flat.

B. 5 lb/A: 6700 mg. of EPTC 6E (75.5%) was diluted with 500 ml. of deionized water so that 2 ml. equals 5 lb/A/plastic flat.

Additive stock solutions were prepared by diluting 102 mg. of technical material with 10 ml. of acetone 1% Tween 20 (polyoxyethylene sorbitan monolaurate) so that 2 ml. equals 5 lb/A/flat.

After the soil was treated with both herbicide and additive, the soil was transferred from the mixer back into the flat where it was then prepared for seeding. The initial step in preparation was to remove a one pint sample of soil from each flat to be retained and used to cover the seeds after planting. The soil was then leveled and rows one-quarter inch deep were made in each flat. Flats treated with 5 lb/A of EPTAM were seeded to DeKalb XL-44 corn (Zea maize), US H9 sugarbeets (Beta vulgare), small seeded gray striped sunflower (Helianthus annus), Acala cotton (Gossypium hirsutum), Brag soybeans (Glycine max) and oilseed rape (Brassica napus). Flats treated with 1/2 lb/A of EPTAM were seeded to red oats (Avena byzantina), R-10 milo [sorghum] (Sorghum vulgare), Fremont HRS wheat (Triticum aestivum), giant foxtail (Seteria feberii), Calrose rice (Oryza sativa) and Blue Mariate barley (Hordeum vulgare). Seeds were then covered with the pint soil sample removed prior to seeding.

The flats were then placed on greenhouse benches where temperatures were maintained between 70°-90° F. The soil was watered by sprinkling to assure good plant growth.

Injury ratings were taken 2 and 4 weeks after the treatments were applied. Soil treated with EPTAM alone at 1/2 or 5 lb/A was included to provide a basis for determining the amount of injury reduction provided by the herbicide antidotes. The per cent protection of various representative crops is reported in Table III. The per cent protection is determined by a comparison with flats not treated with the candidate antidote.

                  TABLE III                                                        ______________________________________                                         Multicrop Screen Results                                                       Per Cent Protection                                                            COMPOUND Rate of              % Protection                                     NUMBER   EPTC lb/A  Crop      (2 weeks)                                        ______________________________________                                         31       0.5       barley     56                                                                  rice       30                                               32       0.5       barley     56                                                                  rice       30                                                        5.0       corn       100                                              33       0.5       rice       30                                                                  barley     44                                               34       0.5       barley     88                                                        5.0       corn       100                                              35       0.5       barley     44                                                        5.0       corn       100                                              36       5.0       corn       100                                              37       5.0       corn       100                                              38       0.5       barley     88                                                        5.0       corn       100                                                       5.0       sunflower  50                                               39       5.0       corn       100                                                       5.0       sunflower  25                                                        5.0       oilseed rape                                                                              60                                               40       5.0       corn       100                                                       5.0       sunflower  25                                               41       0.5       barley     50                                                        5.0       corn       100    (4 weeks)                                 42       5.0       corn       56     (4 weeks)                                 43       5.0       corn       93     (4 weeks)                                 44       5.0       corn       28     (4 weeks)                                 45       0.5       barley     50                                                        5.0       sunflower  81                                               46       0.5       rice       100    (4 weeks)                                 47       0.5       rice       100    (4 weeks)                                          0.5       barley     75     (4 weeks)                                          5.0       oilseed rape                                                                              68     (4 weeks)                                 48       0.5       barley     25                                                        5.0       sunflower  67     (4 weeks)                                 49       0.5       sorghum    50                                                        0.5       barley     50                                                        5.0       corn       100    (4 weeks)                                 50       5.0       corn       100    (4 weeks)                                 51       5.0       corn       42     (4 weeks)                                 52       5.0       corn       100    (4 weeks)                                 53       0.5       rice       100    (4 weeks)                                          0.5       barley     50     (4 weeks)                                          5.0       corn       70     (4 weeks)                                 54       0.5       barley     50                                                        5.0       corn       100    (4 weeks)                                 55       0.5       wheat      20     (4 weeks)                                          0.5       barley     100    (4 weeks)                                          5.0       corn       93     (4 weeks)                                 56       0.5       sorghum    10     (4 weeks)                                 57       0.5       barley     50                                                        5.0       corn       100    (4 weeks)                                 58       0.5       rice       100    (4 weeks)                                 59       5.0       corn       93     (4 weeks)                                 60       0.5       rice       100    (4 weeks)                                          5.0       corn       42     (4 weeks)                                 61       0.5       sorghum    40     (4 weeks)                                          0.5       barley     75     (4 weeks)                                          5.0       rice       70     (4 weeks)                                 62       5.0       oilseed rape                                                                              65     (4 weeks)                                 63       0.5       barley     75                                               64       5.0       corn       42     (4 weeks)                                 65       5.0       corn       70     (4 weeks)                                 66       5.0       corn       100    (4 weeks)                                 67       5.0       corn       28     (4 weeks)                                 68       0.5       rice       100    (4 weeks)                                          5.0       corn       93     (4 weeks)                                 69       5.0       corn       42     (4 weeks)                                 70       5.0       corn       100    (4 weeks)                                 71       5.0       corn       70     (4 weeks)                                 72       0.5       rice       100    (4 weeks)                                          0.5       barley     50     (4 weeks)                                          5.0       corn       100    (4 weeks)                                 73       5.0       corn       100    (4 weeks)                                 74       5.0       corn       42     (4 weeks)                                 75       0.5       sorghum    71                                                        0.5       wheat      60                                                        5.0       corn       87                                                        5.0       oilseed rape                                                                              71                                               76       5.0       corn       56     (4 weeks)                                 77       5.0       corn       100    (4 weeks)                                          5.0       sugarbeets 28     (4 weeks)                                 78       0.5       rice       100    (4 weeks)                                          5.0       corn       100    (4 weeks)                                          5.0       sunflower  81     (4 weeks)                                 79       0.5       barley     50                                                        5.0       corn       100    (4 weeks)                                          5.0       sunflower  67     (4 weeks)                                 80       5.0       corn       70     (4 weeks)                                          5.0       oilseed rape                                                                              56     (4 weeks)                                 81       0.5       barley     50     (4 weeks)                                          5.0       sunflower  67     (4 weeks)                                 82       5.0       corn       56     (4 weeks)                                 83       0.5       rice       100    (4 weeks)                                 84       0.5       rice       100    (4 weeks)                                          0.5       barley     50     (4 weeks)                                 85       0.5       rice       100    (4 weeks)                                          0.5       barley     75     (4 weeks)                                          5.0       corn       93     (4 weeks)                                 86       0.5       barley     50     (4 weeks)                                          5.0       corn       100    (4 weeks)                                 87       5.0       corn       93     (4 weeks)                                 88       0.5       barley     45                                               89       0.5       wheat      67                                                        5.0       oilseed rape                                                                              75                                               90       0.5       wheat      15                                               91       0.5       sorghum    50                                                        5.0       corn       84                                               92       5.0       oilseed rape                                                                              75                                               93       5.0       oilseed rape                                                                              75                                               94       5.0       oilseed rape                                                                              75                                               95       5.0       oilseed rape                                                                              75                                               96       5.0       corn       80                                               97       0.5       barley     50                                               98       5.0       sunflower  60                                               99       0.5       barley     88                                               100      5.0       corn       100                                              101      5.0       sunflower  100                                              102      5.0       oilseed rape                                                                              50                                               103      0.5       sorghum    30     (4 weeks)                                          5.0       corn       100                                              104      0.5       rice       30     (4 weeks)                                          0.5       sorghum    30     (4 weeks)                                 105      0.5       wheat      30     (4 weeks)                                          0.5       barley     75     (4 weeks)                                 106      5.0       sunflower  20     (4 weeks)                                 107      0.5       wheat      40     (4 weeks)                                          0.5       barley     60     (4 weeks)                                          5.0       corn       100    (4 weeks)                                 108      5.0       oilseed rape                                                                              75                                               109      5.0       oilseed rape                                                                              75                                               110      5.0       oilseed rape                                                                              75                                               111      5.0       sunflower  60                                               112      5.0       oilseed rape                                                                              75                                               113      5.0       oilseed rape                                                                              67                                               114      5.0       oilseed rape                                                                              33                                               115      0.5       barley     70     (4 weeks)                                          5.0       corn       10     (4 weeks)                                 116      0.5       barley     58     (4 weeks)                                          5.0       sunflower  60     (4 weeks)                                          5.0       corn       100    (4 weeks)                                 117      0.5       barley     58     (4 weeks)                                          5.0       corn       100    (4 weeks)                                 118      0.5       barley     58     (4 weeks)                                          5.0       corn       65     (4 weeks)                                 119      0.5       barley     68     (4 weeks)                                          5.0       corn       100    (4 weeks)                                 120      5.0       sunflower  30                                               121      0.5       rice       67     (4 weeks)                                          5.0       oilseed rape                                                                              60     (4 weeks)                                 122      0.5       barley     58     (4 weeks)                                          5.0       corn       100    (4 weeks)                                 123      0.5       rice       44     (4 weeks)                                 124      0.5       rice       67     (4 weeks)                                          0.5       barley     58     (4 weeks)                                 125      0.5       rice       88     (4 weeks)                                 126      0.5       rice       100                                                       0.5       barley     100                                              127      0.5       rice       78                                                        0.5       barley     64                                               128      0.5       rice       78                                                        0.5       barley     57                                                        5.0       oilseed rape                                                                              60                                               129      0.5       rice       78                                                        0.5       barley     43                                                        5.0       sunflower  100                                              130      0.5       rice       100                                                       0.5       barley     43                                                        5.0       oilseed rape                                                                              40                                                        5.0       soybeans   33                                               131      0.5       barley     43                                                        5.0       sunflower  100                                                       5.0       oilseed rape                                                                              80                                                        5.0       soybeans   47                                               132      0.5       rice       78                                                        0.5       oats       50                                                        0.5       barley     57                                                        5.0       oilseed rape                                                                              100                                                       5.0       corn       58                                               133      0.5       barley     57                                                        0.5       oats       40                                                        5.0       sugarbeets 45                                                        5.0       oilseed rape                                                                              100                                              134      0.5       barley     43                                                        5.0       soybeans   33                                                        5.0       oilseed rape                                                                              80                                               135      0.5       oats       60                                                        5.0       corn       100                                                       5.0       oilseed rape                                                                              100                                              136      0.5       rice       55                                                        0.5       barley     57                                                        5.0       corn       100                                                       5.0       oilseed rape                                                                              80                                               137      0.5       barley     43                                                        5.0       sunflower  70                                                        5.0       soybeans   33                                               138      0.5       rice       78                                                        0.5       barley     71                                                        5.0       oilseed rape                                                                              60                                               139      5.0       sunflower  70                                                        5.0       oilseed rape                                                                              60                                               140      5.0       sunflower  100                                                       5.0       oilseed rape                                                                              60                                                        5.0       soybeans   33                                               141      5.0       soybeans   47                                                        5.0       oilseed rape                                                                              60                                               142      0.5       rice       86                                                        0.5       barley     62.5                                             143      0.5       rice       100                                                       0.5       barley     87.5                                             144      0.5       sorghum    100                                                       0.5       rice       86                                                        0.5       barley     100                                                       5.0       corn       100                                              145      0.5       rice       100                                                       0.5       barley     100                                              146      0.5       barley     75                                                        5.0       oilseed rape                                                                              100                                              147      0.5       rice       72                                                        5.0       corn       88                                               ______________________________________                                    

When used with 2-chloro-2',6'-diethyl-N-(methoxymethyl) acetanilide at 2 lb/A, Compounds No. 1 and 30 at 5 lb/A after 4 weeks gave 100 per cent protection to sorghum. Compoun No. 1 also gave 67 per cent protection to wheat.

When used with 3-(3,4-dichlorophenyl)-1,1-dimethylurea at 1 lb/A, Compounds No. 1 and 30 at 5 lb/A each gave 60 per cent protection to cotton; Compound No. 1 also gave 60 per cent protection to corn; and Compound No. 30 gave 43 per cent protection to corn.

The antidote compounds and compositions of the present invention can be used in any convenient form. Thus, the antidote compounds can be formulated into emulsifiable liquids, emulsifiable concentrates, liquid, wettable powder, powders, granular or any other convenient form. In its preferred form, a non-phytotoxic quantity of an herbicidal antidote compound is admixed with a selected herbicide and incorporated into the soil prior to or after planting the seed. It is to be understood, however, that the herbicides can be incorporated into the soil and thereafter the antidote compound can be incorporated into the soil. Moreover, the crop seed itself can be treated with a non-phytotoxic quantity of the compound and planted into the soil which has been treated with herbicides, or untreated with the herbicide and subsequently treated with the herbicide. The addition of the antidote compound does not affect the herbicidal activity of the herbicides.

The amount of antidote compound present can range between about 0.0001 to about 30 parts by weight of antidote compound described herein per each part by weight of herbicide. The exact amount of antidote compound will usually be determined on economic ratios for the most effective amount usable. It is understood that a non-phytotoxic quantity of antidote compound will be employed in the herbicidal compositions described herein.

The herbicides indicated in the tables and elsewhere are used at rates which produce effective control of undesirable vegetation. The range of rates employed herein produce representative results within the recommended amounts set forth by the supplier. Therefore, the weed control in each instance is commercially acceptable within the desired or recommended amount.

It is clear that the classes of herbicidal agents described and illustrated herein are characterized as effective herbicides exhibiting such activity. The degree of this herbicidal activity varies among specific compounds and among combinations of specific compounds within the classes. Similarly, the degree of activity to some extent varies among the species of plants to which a specific herbicidal compound or combination may be applied. Thus, selection of a specific herbicidal compound or combination to control undesirable plant species readily may be made. Within the present invention are prevention of injury to a desired crop species in the presence of a specific compound or combination may be achieved. The beneficial plant species which can be protected by this method is not intended to be limited by the specific crops employed in the examples.

The herbicidal compounds employed in the utility of this invention are active herbicides of a general type. That is, the members of the classes are herbicidally effective against a wide range of plant species with no discrimination between desirable and undesirable species. The method of controlling vegetation comprises applying an herbicidally effective amount of the hereindescribed herbicidal compounds to the area or plant locus where control is desired. The compositions as set forth in this invention include those wherein the preferred active herbicidal compound is selected from EPTC, S-ethyl diisobutyl thiocarbamate, S-propyl dipropyl thiocarbamate, S-2,3,3-trichloroallyl-diisopropyl thiocarbamate, S-ethyl cyclohexyl ethyl thiocarbamate, 2-chloro-2',6'-diethyl-N-(methoxymethyl)acetanilide, S-ethyl hexahydro-1H-azepine-1-carbothioate, 2-chloro-N-isopropylacetanilide, N,N-diallyl-2-chloroacetamide, S-4-chlorobenzyl diethyl thiocarbamate, 2-chloro-4-ethylamino-6-isopropylamino-s-triazine, 2-chloro-4,6-bis(ethylamino)-s-triazine, 2(4-chloro-6-ethylamine-s-triazine-2-yl-amino)-2-methylpropionitrile, 2-chloro-4-cyclopropylamino-6-isopropylamino-s-triazine, 2,4-dichlorophenoxyacetic acid, its esters and salts, and 3-(3,4-dichlorophenyl)-1,1-dimethylurea and combinations thereof.

An herbicide as used herein means a compound which controls or modifies the growth of vegetation or plants. Such controlling or modifying effects include all deviations from natural development; for example, killing, retardation, defoliation, desiccation, regulation, stunting, tillering, stimulation, dwarfing and the like. By "plants," it is meant germinant seeds, emerging seedlings, and established vegetation, including the roots and above-ground portions. 

What is claimed is:
 1. An herbicidal composition comprising an active thiocarbamate herbicidal compound and an antidote therefor corresponding to the formula ##SPC4##in which X is oxygen or sulfur, R is haloalkyl having 1 to 10 carbon atoms, inclusive, and the term halo includes chloro and bromo substitutions, alkyl having 1 to 10 carbon atoms, inclusive, or alkylthio having 1 to 4 carbon atoms, inclusive; R₁, R₂, R₃, R₄, R₅ and R₆ are independently selected from the group consisting of hydrogen, lower alkyl having 1 to 4 carbon atoms, inclusive, alkoxyalkyl having a total of 2 to 4 carbon atoms, inclusive, and lower alkylol having 1 to 4 carbon atoms, inclusive.
 2. The composition as set forth in claim 1 wherein X is oxygen, R is haloalkyl, R₁ is lower alkyl, R₂ is lower alkyl and R₃, R₄, R₅ and R₆ are each hydrogen.
 3. A composition according to claim 2 in which R is dichloromethyl, R₁ is methyl and R₂ is methyl.
 4. A composition according to claim 2 in which R is monochloromethyl, R₁ is methyl and R₂ is methyl.
 5. A composition according to claim 2 in which R is tribromomethyl, R₁ is methyl and R₂ is methyl.
 6. A composition according to claim 2 in which R is monochloromethyl, R₁ is methyl and R₂ is ethyl.
 7. A composition according to claim 2 in which R is dichloromethyl, R₁ is methyl and R₂ is ethyl.
 8. A composition according to claim 2 in which R is trichloromethyl, R₁ is methyl and R₂ is ethyl.
 9. A composition according to claim 2 in which R is 1-bromoethyl, R₁ is methyl and R₂ is ethyl.
 10. A composition according to claim 2 in which R is tribromomethyl, R₁ is methyl and R₂ is ethyl.
 11. A composition according to claim 2 in which R is monobromomethyl, R₁ is methyl and R₂ is ethyl.
 12. A composition according to claim 2 in which R is 1,2,3,4-tetrabromopentyl, R₁ is methyl and R₂ is methyl.
 13. A composition according to claim 2 in which R is 2-chloroethyl, R₁ is methyl and R₂ is methyl.
 14. A composition according to claim 2 in which R is 1,2-dibromoethyl, R₁ is methyl and R₂ is ethyl.
 15. A composition according to claim 2 in which R is 1,2-dibromoethyl, R₁ is methyl and R₂ is methyl.
 16. A composition according to claim 2 in which R is 1,2-dibromoethyl, R₁ is methyl and R₂ is t-butyl.
 17. A composition according to claim 2 in which R is dichloromethyl, R₁ is methyl and R₂ is t-butyl.
 18. A composition according to claim 2 in which R is tribromomethyl, R₁ is methyl and R₂ is t-butyl.
 19. A composition according to claim 2 in which R is dichloromethyl, R₁ is methyl and R₂ is i-propyl.
 20. A composition according to claim 2 in which R is 2-bromoethyl, R₁ is methyl and R₂ is methyl.
 21. A composition according to claim 2 in which R is ω-bromodecyl, R₁ is methyl and R₂ is methyl.
 22. A composition according to claim 2 in which R is 3-chloropropyl, R₁ is methyl and R₂ is methyl.
 23. A composition according to claim 2 in which R is 2-chloropropyl, R₁ is methyl and R₂ is methyl.
 24. A composition according to claim 2 in which R is 1-bromopropyl, R₁ is methyl and R₂ is methyl.
 25. A composition according to claim 2 in which R is 1-bromobutyl, R₁ is methyl and R₂ is methyl.
 26. A composition according to claim 2 in which R is 5-bromopentyl, R₁ is methyl and R₂ is methyl.
 27. A composition according to claim 1 wherein X is oxygen, R is alkyl, R₁ is lower alkyl, R₂ is lower alkyl and R₃, R₄, R₅ and R₆ are each hydrogen.
 28. A composition according to claim 27 in which R is hexyl, R₁ is methyl and R₂ is methyl.
 29. The composition as set forth in claim 1 wherein X is sulfur, R is haloalkyl, R₁ is lower alkyl, R₂ is lower alkyl and R₃, R₄, R₅ and R₆ are each hydrogen.
 30. A composition according to claim 29 in which R is dichloromethyl, R₁ is methyl and R₂ is methyl.
 31. A composition according to claim 29 in which R is trichloromethyl, R₁ is methyl and R₂ is methyl.
 32. A composition according to claim 29 in which R is dibromomethyl, R₁ is methyl and R₂ is methyl.
 33. A composition according to claim 29 in which R is 1-bromoethyl, R₁ is methyl and R₂ is methyl.
 34. A composition according to claim 29 in which R is 2-bromoethyl, R₁ is methyl and R₂ is methyl.
 35. A composition according to claim 29 in which R is 1,2-dibromoethyl, R₁ is methyl and R₂ is methyl.
 36. A composition according to claim 29 in which R is 3-chloropropyl, R₁ is methyl and R₂ is methyl.
 37. A composition according to claim 29 in which R is 2-chloropropyl, R₁ is methyl and R₂ is methyl.
 38. A composition according to claim 29 in which R is 1-bromopropyl, R₁ is methyl and R₂ is methyl.
 39. A composition according to claim 29 in which R is 1-bromobutyl, R₁ is methyl and R₂ is methyl.
 40. A composition according to claim 29 in which R is 5-bromopentyl, R₁ is methyl and R₂ is methyl.
 41. A composition according to claim 29 in which R is dichloromethyl, R₁ is methyl and R₂ is ethyl.
 42. A composition according to claim 29 in which R is 1-bromoethyl, R₁ is methyl and R₂ is ethyl.
 43. A composition according to claim 29 in which R is 2-bromoethyl, R₁ is methyl and R₂ is ethyl.
 44. A composition according to claim 29 in which R is monochloromethyl, R₁ is methyl and R₂ is ethyl.
 45. The composition as set forth in claim 1 wherein X is oxygen, R is haloalkyl, R₁ is lower alkyl, R₂ is lower alkyl, R₅ is lower alkyl and R₃, R₄ and R₆ are each hydrogen.
 46. A composition according to claim 45 in which R is tribromomethyl, R₁ is methyl, R₂ is methyl and R₅ is methyl.
 47. A composition according to claim 45 in which R is monochloromethyl, R₁ is methyl, R₂ is methyl and R₅ is methyl.
 48. A composition according to claim 45 in which R is dichloromethyl, R₁ is methyl, R₂ is methyl and R₅ is methyl.
 49. A composition according to claim 45 in which R is 1-bromoethyl, R₁ is methyl, R₂ is methyl and R₅ is methyl.
 50. A composition according to claim 45 in which R is monobromomethyl, R₁ is methyl, R₂ is methyl and R₅ is methyl.
 51. A composition according to claim 45 in which R is 1,2-dibromoethyl, R₁ is methyl, R₂ is methyl and R₅ is methyl.
 52. A composition according to claim 45 in which R is 2-chloropropyl, R₁ is methyl, R₂ is methyl and R₅ is methyl.
 53. A composition according to claim 45 in which R is 1-bromopropyl, R₁ is methyl, R₂ is methyl and R₅ is methyl.
 54. A composition according to claim 45 in which R is 1-bromobutyl, R₁ is methyl, R₂ is methyl and R₅ is methyl.
 55. A composition according to claim 45 in which R is 3-chloropropyl, R₁ is methyl, R₂ is methyl and R₅ is methyl.
 56. A composition according to claim 45 in which R is 5-bromopentyl, R₁ is methyl, R₂ is methyl and R₅ is methyl.
 57. The composition as set forth in claim 1 wherein X is oxygen, R is haloalkyl, R₁ is lower alkyl, R₂ is lower alkyl, R₃ is lower alkyl, R₄, R₅ and R₆ are each hydrogen.
 58. The composition as set forth in claim 1 wherein X is oxygen, R is haloalkyl, R₁ is lower alkyl, R₂ is lower alkyl, R₃ is lower alkyl and R₄ is lower alkyl, R₅ and R₆ are each hydrogen.
 59. The composition as set forth in claim 1 wherein X is oxygen, R is haloalkyl, R₁, R₂, R₃, R₄ and R₅ are each independently lower alkyl and R₆ is hydrogen.
 60. The composition as set forth in claim 1 wherein X is oxygen, R is haloalkyl, R₁ is alkoxyalkyl, R₂, R₃, R₄, R₅ and R₆ are each hydrogen.
 61. The composition according to claim 60 in which R is dichloromethyl and R₁ is methoxymethyl.
 62. The composition as set forth in claim 1 wherein X is oxygen, R is haloalkyl, R₁ is lower alkyl, R₅ is lower alkyl and R₂, R₃, R₄ and R₆ are each hydrogen.
 63. The composition as set forth in claim 1 wherein X is oxygen, R is haloalkyl, R₃ is lower alkyl and R₁, R₂, R₄, R₅ and R₆ are each hydrogen.
 64. The composition as set forth in claim 1 in which X is oxygen, R is dichloromethyl, R₁, R₂, R₃, R₄, R₅ and R₆ are each hydrogen.
 65. The composition as set forth in claim 1 in which X is sulfur, R is dichloromethyl, R₁ is ethyl, R₂, R₃, R₄, R₅ and R₆ are each hydrogen.
 66. The method of protecting a crop from injury due to a thiocarbamate herbicide, comprising applying to the crop seed prior to planting a non-phytotoxic antidotally effective amount of a compound corresponding to the formula ##SPC5##in which X is oxygen or sulfur; R is haloalkyl, alkyl, alkylthio; and R₁, R₂, R₃, R₄, R₅ and R₆ are independently selected from the group consisting of hydrogen, lower alkyl, alkoxyalkyl and lower alkylol.
 67. The method of protecting a crop from injury due to a thiocarbamate herbicide, comprising preplant incorporation in the soil in which said crop is to be planted, a non-phytotoxic antidotally effective amount of a compound corresponding to the formula ##SPC6##in which X is oxygen or sulfur; R is haloalkyl, alkyl, alkylthio; and R₁, R₂, R₃, R₄, R₅ and R₆ are independently selected from the group consisting of hydrogen, lower alkyl, alkoxyalkyl and lower alkylol. 